EP0017284A2 - Herstellung ungesättigter Ketone - Google Patents

Herstellung ungesättigter Ketone Download PDF

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Publication number
EP0017284A2
EP0017284A2 EP80200262A EP80200262A EP0017284A2 EP 0017284 A2 EP0017284 A2 EP 0017284A2 EP 80200262 A EP80200262 A EP 80200262A EP 80200262 A EP80200262 A EP 80200262A EP 0017284 A2 EP0017284 A2 EP 0017284A2
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EP
European Patent Office
Prior art keywords
process according
general formula
carbon atoms
group
compound according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP80200262A
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English (en)
French (fr)
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EP0017284A3 (de
Inventor
Aaldert Johannes De Jong
Antonius Johannes Cornelis Van Seters
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Publication of EP0017284A2 publication Critical patent/EP0017284A2/de
Publication of EP0017284A3 publication Critical patent/EP0017284A3/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
    • C07C45/676—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton by elimination of carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones

Definitions

  • the present invention relates to a process for the preparation of unsaturated ketones which are of interest as intermediates in the preparation of perfumes and/or vitamins.
  • the present invention relates in particular to a process for the preparation of 5-hexen-2-one (allylacetone).
  • allylacetone can be prepared from acetone and allylchloride using a large molar excess of acetone (more than 10 moles per mole of allylchloride) in the presence of a substantial amount of caustic alkali (1.0 - 3.0 mole) and a small amount of sodium iodide.
  • the reaction product contains a substantial amount of the unwanted product mesityloxide as well as of higher condensation products up to an amount as high as fifteen times the amount of initially produced allylacetone.
  • the high ratio of solvent/reagent required is highly undesirable in a commercial process.
  • diketo esters can be obtained by reacting beta-oxo esters and alph-haloketones in solution in the presence of an alkalimetal carbonate and/or a tertiary amine.
  • alkalimetal carbonate and/or a tertiary amine an alkalimetal carbonate and/or a tertiary amine.
  • unsaturated ketones and in particular 5-hexen-2-one can be prepared by reacting a beta-keto ester and an allylhalide in the presence of an alkali metal carbonate, optionally in the presence of a solvent, followed by hydrolysing the unsaturated keto ester obtained and decarboxylating the unsaturated keto acid formed.
  • the present invention therefore relates to a process for the preparation of unsaturated ketones according to the general formula: wherein R 1 represents an alkyl, cycloalkly, aryl, aralkyl or alkaryl group, and R 2 ,R 3 and R 4 , each of which may be the same or different represent a hydrogen atom or an alkyl, cycloalkyl, aryl, aralkyl or alkaryl group or R3 and R 4 together represent a tetra-or pentamethylene group, which comprises reacting a compound of the general formula: wherein R has the meaning as defined hereinabove and R represents an alkyl group or a cycloalkyl group, with a compound according to the general formula: wherein R 2 , R 3 and R 4 have the meaning as defined hereinabove and X represents a chlorine, bromine or iodine moiety in the presence of an alkalimetal carbonate followed by hydrolysing the unsaturated keto ester obtained and decarboxy
  • the process according to the present invention relates in particular to a process for the preparation of unsaturated ketones according to the general formula I by reacting a compound according to the general formula II in which R 1 represents an alkyl group of up to 10 carbon atoms or a cycloalkyl group having of from 5 to 7 carbon atoms or an aryl .
  • R represents a linear branched alkyl group of up to 10 carbon atoms or a cycloalkyl group of from 5 to 7 carbon atoms with a compound according to the general formula III wherein R 2 ,R 3 and R 4 each of which may be the same or different represent a hydrogen atom or an alkyl group of up to 10 carbon atoms, or a cycloalkyl group of from 5 to 7 carbon atoms or an aryl, alkaryl or alkaryl group of up to 10 carbon atoms and X represents a chlorine, bromine or iodine moiety in the presence of an alkalimetal carbonate followed by hydrolysing the unsaturated keto ester obtained and decarboxylating the unsaturated keto acid formed.
  • the present invention relates preferably to a process for the preparation of unsaturated ketones according to the general formula I by reacting a compound according to the general formula II in which R represents an alkyl group of up to 4 carbon atoms, for instance a methyl, ethyl or isopropyl group; and R represents a linear or branched alkyl group of up to 6 carbon atoms, for instance a methyl, ethyl or isobutyl group with a compound according to the general formula III in which R 2 ,R 3 and R 4 each of which may be the same or different represent a hydrogen atom or an alkyl group of up to 6 carbon atoms, such as a methyl, ethyl or isopropyl group and X represents a chlorine moiety in the presence of sodium and/or potassium carbonate and hydrolysing the unsaturated keto ester obtained and decarboxylating the unsaturated keto acid formed.
  • R represents an alkyl group of up to 4 carbon atoms,
  • the present invention relates most preferably to a process for the preparation of 5-hexen-2-one by reacting allylchloride and (m)ethyl-3-oxo-butanoate in the presence of potassium carbonate followed by hydrolysing the product 2-acetyl-penten-5-oate which is then decarboxylated.
  • the halogen atom X in the general formula III - i.e. a chlorine, bromine or iodine moiety - is preferably a chlorine atom. Very good results have been obtained using allylchloride as the compound according to formula III.
  • the starting compounds having the general formulae II and III may be used in any desired ratio.
  • Favourable molar ratios between the starting compounds according to the general formulae II and III are usually between 1:1 and 10:1, in particular between 1:1 and 5:1.
  • alkalimetal carbonates those of lithium, sodium, potassium, rubidium and cesium - those of potassium, rubidium and cesium are preferred. Special preference, because of its low price, is given to potassium carbonate.
  • the alkalimetal present in the system is converted with the hydrogen halide liberated during the present process into alkalimetal bicarbonate and alkalimetal halide.
  • the alkali metal bicarbonate is converted with the latter hydrogen halide into alkali metal halide, carbon dioxide and water. It is preferable to keep the reaction medium anhydrous since water has a retarding effect on the first step of the present process. It is recommended to use a molar ratio of at least 1 and preferably between 1: and 2:J between the alkali metal carbonate and the compound according to the general formula III.
  • alkali metal carbonate particles The smaller the size of the alkali metal carbonate particles, the less chance there is, if molar ratios between the alkali metal carbonate and the compound according to the general formula III in excess of 1 are used, of formed alkali metal bicarbonate and hydrogen halide forming water; the smaller the particle size of the remaining alkali metal carbonate, the more readily it is accessible to hydrogen halide.
  • the formation of unsaturated keto ester therefore takes place all the more rapidly and the selectivity to unsaturated keto ester is accordingly all the higher as alkali metal particles of smaller dimensions are used.
  • Alkali metal carbonate particles of which, the largest dimension is smaller than 0.2 mm are very useful.
  • Particles of which the largest dimension is larger than 0.2 mm, for example between 0.5mm and 2.5 mm, can be employed, but preferably in combination with the use of molar ratios of between, for example 2:1 and 5:1 between alkali metal carbonate and compound according to the general formula III.
  • the use of potassium carbonate is preferred for economic reasons.
  • the process according to the present invention can be carried out in the presence or in the absence of a solvent. It has been found that it may be advantageous to add an inert solvent prior to the reaction or during the course of the reaction which is carried out by just mixing the ingredients, in order to prevent serious stirring problems. A reduced stirring, however, does not contribute adversely against the yield of the reaction concerned.
  • Suitable solvents which can be used in the process according to the present invention comprise ketones, ethers and hydrocarbons. Ketones are preferred . Examples of ketones are acetone, 2-butanone, 2-pentanone, 3-pentanone, 3-methyl-2-butanone, 3-methyl-2-pentanone and 2-hexanone. Acetone is especially preferred. Examples of ethers which can be suitably applied as solvents comprise dimethoxyethane, diethoxy ethane, dioxane, dimethyl ether, diethyl ether and tetrahydrofuran whereas hydrocarbon solvents are examplified by benzene, toluene, ethylbenzene and the xylenes. Also mixtures of solvents can be suitably applied.
  • the process according to the present invention is to be carried out by thoroughly mixing the ingredients. This may be achieved, for example, by means of a stirring device, e.g. a propeller mixer and/or by refluxing the solution. Stirring is especially preferred when working in the absence or in the presence of a minor amount of a appropriate solvent. As a rule the reaction proceeds readily at atmospheric pressure, but super-atmospheric or sub-atmospheric pressures can be used as well.
  • the concentrations in which the compounds having the formula II and III are used are not critical and may vary between wide limits.
  • the concentrations to be chosen in a given case naturally depend on the solubility of the starting compound(s) in the solvent and may be, for example, between 0.5 and 4.0 mole.
  • phase transfer catalysts comprise quaternary "onium" salts such as quaternary ammonium or sulphonium compounds as well as 18-crown-6- or related compounds. Very good results can be obtained using quaternary ammonium salts such as tetra-alkylammonium chlorides or bromides, e.g.
  • quaternary "onium” compounds can be applied in amounts similar to the inorganic iodine compounds.
  • the process according to the present invention can be carried out batchwise as well as continuously or semi-continuously.
  • the working up of the resultant reaction product which comprises as main product an unsaturated keto ester and converting it into a compound according to general formula I may be carried out in a conventional manner.
  • remaining alkali. metal carbonate and salts formed from the alkali metal carbonate are first removed, e.g. by filtering or centrifuging.
  • the solvent, if any and any starting materials which may still be present may subsequently be removed, e.g. by means. of distillation, if desired at subatmospheric pressure.
  • the unsaturated keto ester obtained can be converted into the corresponding compound according to formula I by methods known in the art; e.g. by converting the unsaturated keto ester with an alkali solution into the corresponding alkali salt which is decarboxylated under the reaction conditions using for instance hydrochloric acid or sulphuric acid to give the final compound according to formula I.
  • Aqueous, sodium hydroxide in concentrations up to about 30%, preferably in the range of from 5-15% can be suitably applied in the saponification step.
  • Example I The experiment described in Example I was repeated with the exception that 0.3 mole of methylacetoacetate (MAA) and 0.2 mole of allylchloride were used. After working up 5-hexen-2-one appeared to have been formed (69.5% calculated on allychloride). Repeating the experiment using 0.25 mole of MAA per 0.2 mole of allylchloride afforded 74.4% of 5-hexen-2-one together with a small amount of dicondensation product.
  • MAA methylacetoacetate
  • allylchloride methylacetoacetate
  • Example I The experiment described in Example I was repeated with the exception, that 0.3 mole of ethylacetoacetate and 0.2 mole of allylchloride were used. After working up 5-hexen-2-one had been formed(54.0% calculated on allylehloride) together with about 1% of dicondensation product.
  • Example II The experiment described in Example I was repeated, this time replacing the solvent acetone with the same amount of toluene which also contained a very small amount of trimethylbenzylammonium chloride. After 16 hours the reaction mixture was worked up and 5-hexen-2-one had been formed (70% calculated on allylchloride) together with only 2% of dicondensation product.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP80200262A 1979-04-03 1980-03-21 Herstellung ungesättigter Ketone Withdrawn EP0017284A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB7911678 1979-04-03
GB7911678 1979-04-03

Publications (2)

Publication Number Publication Date
EP0017284A2 true EP0017284A2 (de) 1980-10-15
EP0017284A3 EP0017284A3 (de) 1980-10-29

Family

ID=10504311

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80200262A Withdrawn EP0017284A3 (de) 1979-04-03 1980-03-21 Herstellung ungesättigter Ketone

Country Status (2)

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EP (1) EP0017284A3 (de)
JP (1) JPS55133328A (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4496766A (en) * 1982-05-04 1985-01-29 Nippon Zeon Co. Ltd. Process for production of α,β-unsaturated ketones

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL7216590A (de) * 1972-12-07 1974-06-11
JPS5858335B2 (ja) * 1975-08-20 1983-12-24 住友化学工業株式会社 アルフア − チカンアセトンノセイゾウホウ
GB1597866A (en) * 1977-08-12 1981-09-16 Otsuka Kagaku Yakuhin 2-cyclopentone derivatives

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4496766A (en) * 1982-05-04 1985-01-29 Nippon Zeon Co. Ltd. Process for production of α,β-unsaturated ketones

Also Published As

Publication number Publication date
EP0017284A3 (de) 1980-10-29
JPS55133328A (en) 1980-10-17

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